3-pyridylethyl 2, 4-oxazolidinediones and process



United States Patent C 3'-PYRIDYLETHYL 2,4-OXAZOLIDINEDIONES AND PROCESS Seymour L. Shapiro, Hastings-on-Hudson, Louis Freedman, Bronxville, and Ira" M. Rose, Yonkers, N. Y., assignors to U. S. Vitamin Corporation, New York, Y., a corporation of Delaware No Drawing. Application November 6, 1957 Serial N 0. 694,731

8 Claims. (Cl. 167-52) compositions of matter pyridylethylated derivatives of oxazolidinediones and especially pyridylethylated oxazolidinediones which bear a substituent, or substituents, in the -position of the oxazolidinedione ring.

A still further object of the invention is the provision of a process for the preparation of a pyridylethylated oxazolidinedione by reacting a pyridine having a vinyl group in the 2-, 4- or 6-po-sition of the pyridine ring with an oxazolidinedione having available the acidic hydrogen on the. nitrogen in the 3-position of the oxazolidinedione system and a special object of theinvention is the provision of a process for the preparation of pyridylethylated oxazolidinediones by reacting a member of the group consisting of.2vinyl pyridine, 2-vinyl-5-ethylpyridine and 4-vinylpyridine with a 1,3-oXazolidine-2,4-dione, and with 5-monosubstituted and 5,5-disubstituted derivatives thereof.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others, and the composition possessing the features, properties and the relation of constituents which are exemplified in the following detailed disclosure and the scope of the invention will be indicated in the claims.

In the practice of the invention an oxazolidinedione may be prepared by reacting a pyridine having a vinyl group in the 2, 4- or 6-position of the pyridine ring with an oxazolidinedione having available the acidichydrogen on the nitrogen in the 3-position of the oxazolidinedione system. The reaction which takes place may be illustrated by the following equation:

-O R: R2 0 in which R andR are members of the group consisting of hydrogen, lower alkyl, cycloalkyl, aryl, aralkyl and structures wherein R plus R is an alkylene chain and a methyl substituted alkylene chain joined at the S-carbon atom of the oxazolidinedione ring system said alkylene chain having a carbon content C l-C It will be-recog+ nized that when R and R are different, that the carbon atom at position 5 of the oxazolidinedione'ring system is asymmetrioandcapable of resolutioni'into d and l 'forms.

These forms separated or unseparated are'to be con sidered within the purview of this. invention.

Further, the alkyl group may have a carboncontent Cy-C hence methyltoheptyl'; the cycloalkyl may have a carbon content C -C thuscyclopropyl to cyclohex-yl; the aryl group maybe phenyl and tolyil, and a substituent on the aryl may be halogen, hydroxyl, alkyl, alkoxy and aralkyl containing from 7-8 carbon atoms.- Moreover, R and R may be satisfied by a single cycloalkyl group" having a carbon content of C -C wherein R and R2 may be joined as a methylene group bridge of from 4-6 carbon atoms having the structure Py having the meaning given below.

When the spirosubstituent derived from the methylene chain formed by the juncture of R plus R in the compounds described immediately above, bears a substituent such as methyl, then two diastereoisomeric forms of the compound are possible. While we have not definitely determined the exact stereochemical relationship of the two forms, it is likely'that in one instance the oxygen atom at the 1 position of the oxazolidinedione ring system is attached as an equatorial group to the cyclothexyl ring, whereas in the other isomer the oxygen at position 5 of the ring is attached as an axial group to the cyclohexyl ring. These respective forms are structurally depicted as follows:

I CH2CHzPy (0 attached as equatorial group) (0 attached as axial group) these isomers have been separated the two forms'of thereactant oxazolidinedione unsubstituted in the 3-position have been designated as Form A and Form B, and'a're' recognizable by their physical constants. The correspond ing 3-pyridylethylated derivatives in turn are designated in the tables as being derived from the appropriate Form A or Form B of the reactant unsubstituted oxazolidinedione. Because of the tendency of the vinylpyridines to poly-'- merize they ordinarily contain an inhibitor to prevent polymerization during storage. The inhibitor may be removed before reaction of the vinylpy'ridine with the ox azolidinedione, but this, however, is not necessary sincewehave found that the reaction proceeds with the inhibitor present. The reaction conditionsfor effecting the condensation may be varied, thus the reactants may be mixed in equal molar proportions; an excess of either of the reactants may be used; condensation may be .eif'ected in the ab-- sence of a solvent; an inert-solvent may be employed as thereaction medium, and abasic catalyst, such as choline, benzyltrimethylammonium hydroxide, sodium, sodamide -i the vinylpyridine with the oxazolidinedione indicates condensation even at room temperature. However, we have found that the condensation takes place readily by heating the reaction mixture in the temperature range of 120 -170 C. for 0.5-2 hours. Temperatures which are lower lead to markedly slower reaction times, and higher reaction temperatures cause decomposition and polymerization, and thus complicate isolation of the product.

The compounds may be defined as .pyridylethylated oxazolidinediones and are represented by the following general formula:

N-CHg-CHr-PY in which R; and R, have same meaning as above, and Py represents a member of the group consisting of 2- pyridyl, alkyl-substituted-Z-pyridyl said alkyl having a carbon content C -C and 4-pyridyl, and acid addition and quarternary ammonium salts thereof, which are stable and non-toxic. The conventional numbering in this ring system is indicated starting with l at the ring oxygen atom, and proceeding counterclockwise through the oxazole ring. In accordance with this nomenclature the oxygen is in the l-position; the nitrogen is in the 3-position, and the carbonyl oxygens are in the 2- and 4-positions, and hence the substituents R and R, in the 5-position result in the designation B-[pyridylethyl]-5,5,-(R ,R,)'- l,3-oxazolidine-2,4-diones for the ring compounds herein described.

While many of the free bases of the novel pyridylethyl oxazolidinediones have substantial water solubility; for many purposes, and particularly in the instance of the less water soluble free bases, it is desirable to convert the bases to water soluble acid addition salts. which can be used to prepare acid addition salts are mineral acids such as hydrochloric, hydrobromic, nitric, phosphoric and sulfuric acids, and organic acids such as lactic, glycolic, citric, tartaric, and the like. Further,

. reaction product was triturated with hexane.

The acids the bases are readily converted to the acid addition salts by direct interaction of the base with the acid in the presence of a solvent. Moreover, the acid addition salts arepreferably those whose anions are relatively innocuous.,

The bases can also be converted to quaternary ammonium salts derived from the lower alkyl esters of strong inorganicacids, e. g., methyl halides, methyl sulfate, methyl tosylate, ethyl halides, and the like.

As an. illustrative embodiment of a manner in which the invention maybe practiced, the following examples are presented. The required reactant oxazolidinediones having an acidic hydrogen on the nitrogen in the 3-position are conveniently preparable by procedures described in the literature (R. W. Stoughton, J. Am. Chem. Soc. 63:2376, 1941', V. H. Wallingford, M. A. Thorpe and R. W. Stoughton, I. Am. Chem. Soc. 67:522, 1954). The detailed descriptions typify the preparation of the reactant unsubstituted .oxazolidinediones.

EXAMPLEI A mixture of 6.0 g. (0.0594 mole) of 1,3-oxazolidine- 2-4-dione and 7.91 g. (0.0554 mole) of 2-vinyl-5-ethylpyridine in a flask equipped with an air condenser was heated in anoil bath at 150 C. for 2 hours. t a

l 3-(2- IZ-pyfidyl-S-ethyl] ethyl- 1 ,3-oxazolidine 2,4-dione After the reaction mixture had cooled the crystallized The crude product was dissolved in cc. of water; the pH value adjusted to 78 with sodium bicarbonate, and the aqueous solution extracted with three 50 cc. portions of ether. The ether extracts were combined; evaporated; the product dried in a desiccator over phosphorous pentoxide, and then triturated with hexane yielding almost colorless crystals, M. P. 65 C.

EXAMPLE II 3-(2- [4-pyridyl] )ethyl-S-methyl-l ,3 oxazolidine-2,4dione A mixture of 7.61 g. (0.0724 mole) of 4-vinyl pyridine and 10.0 g. (20% excess) of S-methyl-l,3-oxazolidine-2,4- dione was prepared and the reaction mixture became quite warm. After heating in oil bath at C. for 2% hrs. the reaction mixture was distilled and the product obtained as a colorless oil, B. P. 131148 C./.015 mm. from a bath at 186196 C.

EXAMPLE III 3-(2-[2 pyridylDethyl 5,5 dimethyl-I,3-oxazolidine- 2,4-dione EXAMPLE IV 3-(2-[2-pyridyl 5 ethyl])ethyl 5 (3-heptyl)1,3-oxazolidine-2,4-dione A mixture of 5.98 g. (0.03 mole) of 5-(3-heptyl)-l,3- oxazolidine-2,4-dione and 4.0 g. (0.03 mole) of 2-vinyl- S-ethylpyridine was reacted at 150 C. for two hours.

The reaction mixture was cooled; dissolved in 50 cc. of ether, and the product extracted as its hydrochloride by shaking with 60 cc. of 0.75 N hydrochloric acid. The acid aqueous phase after washing with ether was adjusted to pH 7-8 with 4.5 g. of sodium bicarbonate, and the oily product which separated was extracted with two 50 cc. portions of ether. The ether extracts were combined; the ether removed, and 25 ml. of benzene added. After removal of volatiles at 150 C.', the product distilled by short path distillation from a bath at 190-200 C. at -l72 C./0.06 mm. as a colorless oil.

. EXAMPLE V 3-(2-[4-pyridyl] )ethyI-S-phenyl-Z,3-0xaz0lidirze-2,4-di0ne EXAMPLE VI 3-(2-[2-pyridyl-5 -ethy[1) ethyl-5 ,5 -diphenyl-1 ,3-oxaz0lidine-2,4-di0ne hydrochloride A mixture of 5.06 g. (0.02 mole) of 5,5-diphenyl-l,3- oxazolidine-2,4-dione and 2.66 g. (0.02 mole) of 2-vinyl- S-ethylpyridine was reacted at 150 C. for 2 hours.

The cooled reaction product was then converted to the hydrochloride by dissolving in ethanol and bubbling hydrogen chloride gas into the solution. When ether was added the hydrochloride crystallized, M. P. 146-156 C. The hydrochloride was recrystallized from ethyl acetate. Alternatively the hydrochloride can be conveniently prepared by dissolving the reaction product in dilute hy' droehloric acid and adding concentrated hydrochloric endea edac d'with' precipitation of'the hydrochloride due to its bemg sp'aringly soluble inconcentratedhydrochloric acid washed with water, and dried, M. P. 107-108 C.

EXAMPLE VII (Form A). It was unchanged by recrystallization from -Py y y -P y ,3 oxazolidine-2fl-div 5 ethylacetate-hexanez On complete'acidificatiom of 'the' mixture. of 7.79 g. (0044 mole) filtrate, the low melting isomer was obtained, M. PI 76" oxazolidine-2,4-dione and 4:63. g.-(0.044 mole) of 2-vinyl 9 (FFm It was unchanged by recrystallllapyridine was reacted at 150 C. for two hours. The retum-from action mixture was cooled and. dissolved in 50 cc. of ethenand the product extracted from ether with 60cc. of' 0.75 N hydrochloric acid. The acid aqueous phase after washing with ether. was adjusted to pH- 7-8 with'4.5. g. of solid sodiumbicarbonateand the oilyproduct which densation with the vinylpyridines shown in the previous separated extracted into two 50 cc. of ether. The ether examples was obtained by the following sequence of extracts were combined; treated with charcoal; filtered, 15 reactions a few seconds crystallization toino hard' 'needlesof the high melting isomer. This isomer was filtered ofli EXAMPLE 5 p-ch lorophenyl -5 -methyl-] ,3-0xazolidirte -2A-diane This compound which is an initial reactant for con- (Reactant oxazolidinedione),

and the ether removed on a steam bath. Theoily residue The cyanohydrin was. prepared in the. following manner; was'treated with ml. of benzene and the benzene. re- To a cooled (5 10 C.) well stirred mixture of 103.v moved on a steam bath. The residue was stripped of, g. (0.666 mole).of p-ch1oroacetophenone,.60ml. of ether, volatiles by heating at a bath temperature of 192 C. at 0.15 mm. pressure. The residue, not distilling, was the desired product, and was obtained as a viscous oil which is completely soluble in 3 N hydrochloric acid. The product does not distill under ordinary conditions of ture. The ether layer was separated,. dried over magvacuum distillation without some decomposition. nesium sulfate, filtered, and the etherremovedby evapo- EXAMPLE VIII hexane had an M. P. 829-85 C. Recrystallization 3-(2- [4-pyrz'dyl] )ethyl-5,S-diphenyl-],3-0xazolidine-2,4- hexane gavecrystals having-an P 9.2 93 5, C k The dione methiodide alpha-hydroxy amide was prepared in the'following man- A suspension f 21 f 3- 2 4; 1 1 5 5 net. A solutionof55.4 g. (0.33 mole).p-chloroatrolactor' diphenyl-l,3-oxazolidine-2,4-dione in 40 cc. of. ethanol Plmle (as Prepared '5 9f. h r Contamwas treated with 3 cc. of methyl iodide. The solution mg of f l f was saturated y hydrogen thus formed after standing 16 hours, and scratching, Chlorlde 8*} fnalntalnmg temperaiul'ibelow Aftel? i ld a crop f light yellow crystals which were one hour lIllllJO ester hydrochloride separated,- and after rated and rinsed with fresh ethanol, M. P. 166-8 C.

EXAMPLE IX (Alpha-hydroxyamide) cyanide, concentrated hydrochloric acid (140 ml. (1.7

C. for 45 minutes and cooling, the amide crystallized;

5,5-tetramethylene-Ij-oxazolidine zfl dione After solution in 100 ml. (Jf ethyl acetate and filtration (0'.

remove ammonium chloride, and addition of 240 ml. of hexane to the filtrate the amide was obtained having an carbonate was heated under reflux, a solution of 19.4 g. x g' :3 2 E1; 3 gfggi g g xi 58 (0'15 mole) of l'hydroxycyclopentane 'carboxamide in dine-2 4-dione in th e follov in r nanner' S odiiIm metal 50 ml. of hot methanol added, and heating continued for 2 42 (O 105 mole) was dissoied 25ml of refluxing 4 hours. The methanol was removed by distillation; and gi Then 13 6 115 mole) dieth 1 can the residue was dissolved in 100 ml. of water and filtered. b t dd X .The filtrate was washed with two 50 ml. portions of ether i Weref T i 5 3 3 fgfigggff ifig j and then aerated to remove the dissolved ether.1 Afie; 2 E2 ip d f in 25 mlpof methanol was acidification with concentrated hydroch oric acid 3 m 60 and standing 16 hours, the product. was separated washed added. After four hours under reflux,.-the methanol was with water and dried, M. P. 132 -133 C. On extraction of the filtrate with four 50 ml. portions of ether, additional product was obtained.

A mixture of 3.6 g. (0.157 mole) of sodium metal in. 38 ml. of methanol and 20.2 g. (0.172 mole) of diethyl ether, air was passed through the aqueous solution to re move dissolved ether and the product was precipitated EXAMPLE X by slow addition of excess 3- N hydrochloric acid. The

crude product was filtered, washed with water and 5,5-(3 -methylpentametl5y lene)-I,3-0xaz0lzdine-2,4-dzone dried in Vacuo, andyhad an M. P. 103 L106, C Recrys lsomers) tallization from hexane ethyl acetate raised the melting point to 1101l1 C.

EXAMPLE XII 5 -cyclo hexyZ-5 -methyl-I ,3-oxazolidine,2,4-d ione The mixture of stereoisomers was prepared, as in Example IX from 18.5 g. (0.118 mole) of 1-hydroxy-4- methylcyclohexane carboxamide (mixture of isomers). In the final acidification step, careful addition of 3 N bydrochloric acid, the separation point of the two isomers I was taken as that point at which further acid addition ThlS compound WhlCh 1s an rnltral reactant for con- .gave a semipermanent cloudiness which did not clear in 75 densations with vinylpyridines as shown in the previous 100 mlof water, and 82: g. (1.67 moles), of sodium.

mo1es) was added dropwise over'aperiod of 1.7 hours. Stirring was continued for 2 hours: at ambient temperaration. The crystalline product after trituration with.

the second hour an additionalamount was obtained". Upon pyrolysis of the imino ester hydrochloride at 150 removed and the cooled residue was dissolvedin ml.. of water. After washing twice with ml. portions of p reactions.

@ldgcl om-iL-ooocrm on E CH1 0 NH -NH & Na l (Alpha-hydroxy eater) examples was obtained by the following sequence of (Reactant oxaaolidinedione) The alpha-hydroxy ester was prepared in the following manner. Magnesium turnings, 5.35 g. (0.22 mole) were covered with ml. of ether. 5 ml. of cyclohcxyl chloride were added and then a crystal of iodine. Without stirring, the mixture was heated gently till the iodine color had disappeared and the reaction was self sustaining. Then 30 ml. of ether were added and with stirring, the remainder of 23.0 g. (0.20 mole) of cyclohexyl chloride in 60 ml. of ether was added dropwise to maintain gentle reflux. Reflux was maintained for 20 minutes after addition. This solution was filtered through glass wool into a dropping funnel and added, with stirring to a solution of 23.2 g. (0.20 mole) of ethyl pyruvate in 150 ml. of benzene at -5 to 0' over 40 minutes and stirred 40 minutes more. The solution was poured onto crushed ice and enough dilute sulfuric acid added to give an acidic aqueous layer which was removed and extracted twice with ether. The combined organic layers were washed with dilute sodium bicarbonate, dried over magnesium sulfate and solvents removed. On distilling the residue in vacuo, 9.4 g. of product were obtained at 84-100 C./1.l mm.

To a solution of 1.02 g. (0.0445 mole) of sodium metal in 25 ml. of ethanol, 2.66 g. (0.0445 mole) of urea were added and dissolved under reflux. Then 8.9 g. (0.0445 mole) of the alpha-hydroxy ester prepared above were added, rinsed in with 5 ml. of ethanol, and reflux con tinued for 6 hours. Ethanol was removed on a steam bath; the cooled residue dissolved in 100 ml. of water, and the solution washed twice with ether. The aqueous layer was then acidified with 3 N hydrochloric acid and the oily product extracted with ether. The ether was removed on a steam bath, and the residue distilled in vacuo, giving a viscous oil, boiling at 108128 C./ 0.08 mm. When a solution of this material in 130 ml. of hot hexane was allowed to cool slowly, a product crystallized having an M. P. 74.575.5 C.

EXAMPLE x111 3-(2[2pyridyI] ethyl-S- (p-chlorophenyl) -5-methyl-I ,3-

oxazolidine-ZA-dione A mixture of 4.0 g. (0.0177 mole) of 5-p-chlorophenyl- ,S-methyl-l,3-oxazolidine-2,4-dione and 2.04 g. (10% excess) of 2-vinyl pyridine was heated at 150 C. for 2 hours. The acidified (hydrochloric acid) solution of the cooled. residue was washed with ether. The product which precipitated-on the addition of excess sodium biwashed with sodium carbonate was separated, Recrystallizationjrom alarge volumeof hexane raises the M. P. to 6969.5 C.

EXAMPLE IV 3-(2-[2-pyridyl-5-ethyl]) ethyl-5-cyclopr0pyl-5-methyl-1 ,3- oxaz0lidine-2,4-dione A solution of 5.0 g. (10% excess) of S-cyclopropyl-S- methyl-1,3-oxazolidine-2,4-dione and 4.0 g. (0.03 mole) of 2-vinyl-5-ethyl pyridine was heated at 150 C. for two hours. The acidified (hydrochloric acid) aqueous solution of the cooled residue was washed with ether. After the addition of excess sodium bicarbonate solution the separated oily product was extracted with ether. After removal of the ether, the residue was fractionated by short path distillation and the product, boiling at 158- 168 C./ 0.050 mm., collected.

EXAMPLE XV 3-( 2-[4 -pyridyl]) ethyl-5 ,5 -pentamethylene-1 ,3 -0xaz0l iinc-2,4-dione A mixture of 4.65 g. (0.030 mole) of 5,5-pentamethyl ene-l,3-oxazolidine-2,4-dione and 3.5 g. (10% excess) of 4-vinylpyridine was heated at 150 C. for 2 hours. The melt solidified on cooling and was triturated with hexane yielding 7.42 g. of product M. P. 73.5 75 Recrystallization (hexane) raises the M. P. to 77-77.5 (64%).

EXAMPLE XVI excess) of S-ethyl-S-methyl- 1,3-oxazolidine-2,4-dione and 5.26 g. (0.050 mole) of 4-vinylpyridine was heated at 150 C. for 2 hours. The cooled mass was dissolved in 50 ml. of benzene and bicarbonate solution. After removal of the benzene the residue crystallized, there being obtained a product which melted at 7481 C. Recrystallization (hexane) raises the M. P. to 80-81 C.

The following table, Table I, presents constants and characteristics of compounds representative of those herein disclosed. It will be understood that the description above, and the specific compounds listed in the table and in the preceding examples, are illustrative only, and that they may be varied or modified to a considerable extent without departing from the spirit of the invention or sacrificing the advantages thereof, and therefore the invention is not to be limited to the specific embodiments herein set forth.

A solution of 8.0 g. (10% TABLE I.3-PYRIDYLETHYLATED-OXAZOLIDINE- Py 2-pyridyl A Py 2-pyridyl-5-ethyl :B Py 4-pyridyl: C

Ph phenyl (CoHs) R1 R1 Py Formula B. P., 0.1mm. press. M. I., C.

H H A cmmtmot {Mgzhlodlde 168- H H B CuHuNgO; Methlodlde 14D- B H C CmHmNgO; {Msethiodlde 8 having an M. P. 67'68' C. a

escapee- I 11 12 A large number of intermediates which are not-readily barbiturate sleeping time, depression of central nervous available have been employed in the, preparation of the system,activity and allied pharmacological types of compounds of this invention. The table which follows .activity.

(Table 11) lists the characteristics of these intermediates Typical formulations of the compounds of this invenwhich were reacted by procedures indicated in the 5 tion include tablets for oral use, sterile solutions and examples. suppositories.

TABLE II.-TABULAR REPRESENTATION 0E INITIAL BEAU-PANTS R|\ /OH R]\ /0H R1 /0 /C\ /CCNH: R/ 1;, ON a. ii NH Kit (cysnhydrin) Xb (slphe-hydroxy- Xc (orazolidineamide) dione) CHs-- Xb 78-84 D on- Xc sis-9610.03

(a) This ester is described in no example.

(0) ph e unis pheigl (CeHs).

2e) --(0 -CH K;- derivntives are all one form starting with cynnhydrin. d) -(CHs)r-CHCHr-CH:- derivatives are a mixture of two forms.

The foregoing table presents a detailedtabulation of the This application is a continuation-in-part of our coproperties of less readily available starting materials and 70 pending application Serial No. 626,284, filed December 5, the reactant 3-unsubstituted oxazaolidinediones derived 1956, nowabandoned.

from them. The invention accordingly comprises the several steps The compounds of this invention are useful therapeutic and the relation of one or more of such steps with respect agents and have been found to have--anticonvulsant,- to each of the others and the composition possessing the analgesic, hypnotic. ganglionic blocking, prolongation of 75 features, properties and the relation of constituents which are exemplified in the following detailed disclosure and the scope of the invention will be indicated in the claims.

It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention, which as a matter of language might be said to fall therebetween.

Having described our invention, what we claim as new and desire to secure by Letters Patent is:

1. As a composition of matter a member of the group consisting of oxazolidine 2,4-dione having the formula wherein Py is a member of the group consisting or 2- pyridyl, alkyl-substituted-Z-pyridyl, said alkyl having a carbon content C C and 4-pyridyl, and R and R are members of the group consisting of hydrogen, lower alkyl, cycloalkyl, said cycloalkyl having a carbon content C -C aralkyl, said aralkyl being hydrocarbon and having a carbon content C C phenyl, and structures wherein R plus R is an alkylene chain and a methyl substituted alkylene chain joined at the S-carbon atom of the oxazolidinedione ring system said alkylene chain having a carbon content C -C and acid addition and quaternary ammonium salts thereof.

2. A composition of matter, comprising the compound of claim 1, and a non-toxic pharmaceutical carrier therefor, for oral administration.

3. A composition of matter as defined in claim 1 the free base wherein R is methyl; R is hydrogen; and Py is 4-pyridyl.

4. A composition of matter as defined in claim 1 the O N-CHg-CH 5. A composition of matter as defined in claim 1 the free base wherein R is ethyl; R is methyl and Py is 4-pyridyl.

6. A composition of matter as defined in claim 1 the free base wherein R is methyl; R is methyl and Py is 4-pyridyl.

7. A composition of matter as defined in claim 1 the free base wherein R is p-chlorophenyl; R is methyl and Py is Z-pyridyl.

8. A process for the preparation of a 3-pyridylethylated 1,3-oxazolidine 2,4-dione which comprises reacting a member of the group consisting of 2-viny1pyridine, 2-vinyl-5-ethylpyridine and 4-viny1pyridine and a 1,3- oxazolidine-2,4-dione having the formula R1 0 R2 I I O NH wherein R and R are members of the group consisting of hydrogen, lower alkyl, cycloalkyl, said cycloalkyl having a carbon content C -C aralkyl, said aralkyl being hydrocarbon and having a carbon content C -C phenyl, and structures wherein R plus R is an alkylene chain and a methyl substituted alkylene chain joined at the S-carbon atom of the oxazolidinedione ring system said alkylene chain having a carbon content C -C and recovering the resultant 3-pyridylethylated oxazolidinedione.

No references cited. 

1. AS A COMPOSITION OF MATTER A MEMBER OF THE GROUP CONSISTING OF OXAZOLIDINE 2,4-DIONE HAVING THE FORMULA 